Planarization method and planarization apparatus

ABSTRACT

According to one embodiment, a planarization method and a planarization apparatus are provided. In the planarization method, a work surface of a work piece is planarized by bringing the work surface of the work piece containing a silicon oxide film and a surface of a solid plate onto which hydrogen ions are adsorbed, into contact or extremely close proximity with one another in a state in which a process liquid containing fluorine ions is supplied to the surface of the solid plate.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No. 14/021,413filed Sep. 9, 2013, and is based upon and claims the benefit of priorityfrom Japanese Patent Application No. 2013-020943, filed Feb. 5, 2013;the entire contents of each of which are incorporated herein byreference.

FIELD

Embodiments described herein relate generally to a planarization methodand a planarization apparatus.

BACKGROUND

In recent years, in the manufacturing of semiconductor devices, theChemical Mechanical Polishing (CMP) method is in wide use forplanarizing insulating films, metal films, polycrystalline silicon filmsor the like formed to fill in grooves formed on a substrate. The CMPmethod is a method which supplies a polishing agent (a slurry)containing abrasive grains and a chemical solution onto a polishingcloth and brings a work piece into contact with the polishing cloth,thereby planarizing a work surface by combining the chemical action ofthe chemical solution and the mechanical action of the abrasive grains.However, in the CMP method, mechanical damage caused by the abrasivegrains may not be avoided, and there is a problem in that abrasiondamage occurs on the work surface.

In relation to the problem, a method is being considered which avoidsabrasion damage to the work surface by using a process liquid which doesnot contain the abrasive grains. For example, there is a method ofplanarizing a metal film surface by using the temperature rise of aportion in contact with the polishing cloth to chemically dissolve theheated portion with the process liquid. There is also a method ofplanarizing a silicon film, a silicon carbide film, a gallium nitridefilm, an aluminum oxide film, a metal film, or the like by bringing thework piece into contact with a solid plate formed from a catalyst andchemically dissolving a contacting portion using the process liquid.

However, there is no method proposed which planarizes a silicon oxidefilm essential for the manufacturing of semiconductor devices.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view showing a configuration example of aplanarization apparatus which planarizes a silicon oxide film accordingto a first embodiment;

FIG. 2 is a cross section view showing the processes and the principlesof the planarization of the silicon oxide film according to the firstembodiment;

FIG. 3 is a cross section view continuing from FIG. 2, which shows theprocesses and the principles of the planarization of the silicon oxidefilm according to the first embodiment;

FIG. 4 is a perspective view showing a configuration example of aplanarization apparatus which planarizes a silicon oxide film accordingto a second embodiment;

FIG. 5 is a plan view showing the configuration example of theplanarization apparatus which planarizes a silicon oxide film accordingto the second embodiment:

FIG. 6 is a cross section view showing the manufacturing process of theSTI structure of a semiconductor device according to the firstembodiment and the second embodiment;

FIG. 7 is a cross section view continuing from FIG. 6, which shows themanufacturing process of the STI structure of the semiconductor device;

FIG. 8 is a cross section view continuing from FIG. 7, which shows themanufacturing process of the STI structure of the semiconductor device;

FIG. 9 is a cross section view continuing from FIG. 8, which shows themanufacturing process of the STI structure of the semiconductor device.

DETAILED DESCRIPTION

In general, according to one embodiment, a planarization method and aplanarization apparatus are provided which can suppress abrasion damageto a work surface of a work piece containing a silicon oxide film.

According to the embodiment, the planarization method is provided. Inthe planarization method, the work surface of the work piece isplanarized by bringing the work surface of the work piece containing thesilicon oxide film and a surface of a solid plate onto which hydrogenions are adsorbed, into contact or extremely close proximity with oneanother in a state in which a process liquid containing fluorine ions issupplied to the surface of the solid plate.

The present embodiment will be described below with reference to thedrawings. In the drawings, the same portions are assigned the samereference numerals. In addition, duplicate description will be givenwhere necessary.

First Embodiment

The planarization method according to the present embodiment will bedescribed using FIGS. 1 to 3. The present embodiment is an example inwhich a work surface of a work piece 12 which contains a silicon oxidefilm 21 is brought into contact with a surface of a solid plate 11, ontowhich hydrogen (H) ions 23 are adsorbed, within a process liquid 15containing fluorine (F) ions. Therefore the work surface of the siliconoxide film which is in contact with the surface of the solid plate 11 ischemically dissolved, and the work surface is planarized. In the presentembodiment, since mechanical polishing is not necessary, the abrasiondamage to the work surface can be suppressed. The present embodimentwill be described below.

[Planarization Apparatus]

First, the planarization apparatus which performs planarization of asilicon oxide film according to the present embodiment will be describedusing FIG. 1. FIG. 1 is a perspective view showing a configurationexample of the planarization apparatus which planarizes a silicon oxidefilm according to the present embodiment.

As shown in FIG. 1, the planarization apparatus according to the presentembodiment includes a container 10, the solid plate 11, a maintainingportion 13, a heat source 14 and the like.

The container 10 is filled with the process liquid 15 by a processliquid supply unit (not shown). The process liquid 15 is a neutral oracidic solution with a pH of 7 or lower containing fluorine ions 24. Asodium fluoride aqueous solution, a potassium fluoride aqueous solution,an ammonium fluoride aqueous solution, and a mixture of the above and ahydrogen fluoride aqueous solution are used as the process liquid 15.

The solid plate 11 is arranged inside of the container 10 so as to beimmersed in the process liquid 15. The solid plate 11 contains a solidacidic catalyst 22 in at least the surface, and the hydrogen ions 23 areadsorbed onto the surface. A weak acidic cation exchanger is preferableas the solid acidic catalyst 22. An example of the weak acidic cationexchanger is a cation exchanger having a functioning group with an aciddissociation constant of 1.0×10⁻³ or less, specifically, a cationexchanger including a carboxyl group. Accordingly, of the cationscontained in the process liquid 15, the hydrogen ions 23 can beselectively adsorbed. In particular, the hydrogen ions 23 in the processliquid 15 can be selectively adsorbed by giving the cation exchanger afunctioning group with a small acid dissociation constant.

The maintaining portion 13 maintains the work piece 12. The maintainingportion 13 causes the work surface of the work piece 12 to oppose thesurface of the solid plate 11, and can cause the work surface of thework piece 12 and the surface of the solid plate 11 to contact andseparate in relation to one another. The amount of the process liquid 15within the container 10 is adjusted so that a contacting portion betweenthe work surface of the work piece 12 and the surface of the solid plate11 is immersed in the process liquid 15. As described below, the worksurface of the work piece 12 can be planarized by bringing the worksurface (the silicon oxide film 21) of the work piece 12 and the surface(the hydrogen ions 23) of the solid plate 11 into contact or extremelyclose proximity with one another within the process liquid 15 (containsthe fluorine ions 24).

In addition, the solid plate 11 and the maintaining portion 13 are bothrotatable. Even if the hydrogen ions 23 adsorbed onto the surface of thesolid plate 11 are lost due to the contact with the work surface of thework piece 12 by bringing the solid plate 11 and the maintaining portion13 into contact with one another while rotating, the hydrogen ions 23are newly adsorbed onto the surface of the solid plate 11 byre-immersing the solid plate 11 and the maintaining portion 13 in theprocess liquid 15. Furthermore, the movement is not limited to rotation,and the solid plate 11 and the maintaining portion 13 may also be causedto slide in relation to one another.

The heat source 14 is connected to the solid plate 11 and the work piece12 and causes the temperature of the contacting portion to rise.Accordingly, the reaction between the solid plate 11 and the work piece12 to be described below is promoted, and the process speed of the workpiece 12 can be improved. In addition, the reaction between the solidplate 11 and the work piece 12 can also be promoted by raising thetemperature of the process liquid 15 using the heat source 14.

In addition, by bringing the solid plate 11 and the maintaining portion13 into contact with one another while rotating or sliding the solidplate 11 and the maintaining portion 13 as described above, frictionalheat is generated and the temperature of the contacting portion can beraised. In other words, even if the heat source 14 is not used, thetemperature of the contacting portion is raised and the reaction betweenthe solid plate 11 and the work piece 12 can be promoted.

Furthermore, in the present example, an example in which the solid plate11 is fixed within the container 10 and the work piece 12 maintained inthe maintaining portion 13 is moved to bring the work piece 12 intocontact with the solid plate 11, however, the example is not limitedthereto. The work piece 12 and the solid plate 11 may be brought intocontact with one another by fixing the work piece 12 within thecontainer 10 and moving the solid plate 11 maintained in the maintainingportion 13.

[Methods and Principles of Planarization]

Next, the methods and the principles of the planarization of the siliconoxide film according to the present embodiment will be described usingFIGS. 2 and 3. FIGS. 2 and 3 are cross section views which show theprocesses and the principles of the planarization of the silicon oxidefilm according to the present embodiment.

Furthermore, here, an example will be shown in which the work piece 12is formed from a substrate 20 and the silicon oxide film 21 formed on anupper portion thereof, and a surface of the silicon oxide film 21 is thework surface. The substrate 20 is, for example, a semiconductorsubstrate, a glass substrate, or an insulating film or the like formedon a semiconductor substrate. In addition, the solid plate 11 containsthe solid acidic catalyst 22 in at least the surface, and the hydrogenions 23 are adsorbed onto the surface. In addition, the maintainingportion 13 and the heat source 14 in FIG. 1 are omitted.

First, as shown in FIG. 2, the work piece 12 is maintained within theprocess liquid 15 such that the work surface of the work piece 12containing the silicon oxide film 21 opposes the surface of the solidplate 11. The work surface of the silicon oxide film 21 has an irregularshape. The solid acidic catalyst 22 is provided on the solid plate 11.Since the solid acidic catalyst 22 adsorbs the hydrogen ions 23 in theprocess liquid 15, the hydrogen ions 23 are adsorbed onto the surface ofthe solid plate 11. In addition, the hydrogen ions 23 may also beadsorbed onto the surface of the solid plate 11, for example, byimmersing the solid acidic catalyst 22 in a hydrofluoric acid solutionin advance.

Next, as shown in FIG. 3, the work surface of the work piece 12 isbrought into contact or extremely close proximity with the surface ofthe solid plate 11 by moving the work piece 12 within the process liquid15. At this time, at least the contacting portion or a close proximityportion between the work surface of the work piece 12 and the surface ofthe solid plate 11 is immersed in the process liquid 15. Accordingly,the hydrogen ions 23 of the surface of the solid plate 11 are attractedto the oxygen of the work surface, and together with the fluorine ions24 contained within the process liquid 15, dissolve the silicon oxidefilm 21 of the work surface. Within the work surface, since the reactionprogresses preferentially in convex portions of the silicon oxide film21 in contact or extremely close proximity with the solid plate 11, thework surface is planarized. More specifically, silicon dioxide (SiO₂) ofthe work surface, the fluorine ions (F⁻(HF₂ ⁻)) 24 within the processliquid 15 and the hydrogen ions (H+(H₃O⁺)) 23 adsorbed onto the surfaceof the solid plate 11 cause the following reaction.SiO₂+6F⁻+6H⁺→SiF₆ ²⁻+2H⁺+2H₂O  (1)

In other words, the fluorine ions and silicon bonds and are dissolvedwithin the process liquid 15 as hexafluorosilicic acid ions (SiF₆ ²⁻).

Furthermore, here, the term “extremely close proximity” refers tobringing the work surface of the work piece 12 into close proximity withthe surface of the solid plate 11 to an extent at which the hydrogenions 23 dissociate from the surface of the solid plate 11 and thereaction (1) occurs.

In addition, the reaction of reaction formula (1) progresses continuallyat a sufficient speed. Therefore, the movement speed (the pressurepushing against the solid plate 11) of the work piece 12 is notparticularly limited. In other words, the work piece 12 moves at anarbitrary speed and is brought into contact or extremely close proximitywith the solid plate 11.

Furthermore, according to the type of the solid acidic catalyst 22 orthe process liquid 15, there is a case in which a sufficient reactionspeed may not be obtained by just bringing the work piece 12 and thesolid plate 11 into contact or extremely close proximity with oneanother. In this case, the reaction can be caused to proceed efficientlyby raising the temperature of the contacting portion between the workpiece 12 and the solid plate 11.

For example, the heat source 14 is connected to the solid plate 11 andthe work piece 12, therefore the temperature thereof can be raised. Inaddition, the reaction between the solid plate 11 and the work piece 12can also be promoted by raising the temperature of the process liquid 15using the heat source 14.

In addition, by bringing the solid plate 11 and the maintaining portion13 into contact with one another while rotating the solid plate 11 andthe maintaining portion 13, frictional heat is generated and thetemperature can be raised. Furthermore, the movement is not limited torotation, and the solid plate 11 and the maintaining portion 13 may alsobe caused to slide in relation to one another, thereby generatingfrictional heat and raising the temperature.

Subsequently, when the planarization of the work surface finishes, thework piece 12 is separated from the solid plate 11. At this time, thehydrogen ions contained within the process liquid 15 are re-adsorbedonto the surface of the solid plate 11 which the work piece 12 was incontact with, and the surface state becomes the same as before theprocess. In addition, before processing the next work piece, thehydrogen ions 23 may also be adsorbed onto the surface of the solidplate 11, for example, by immersing the solid acidic catalyst 22 in ahydrofluoric acid solution.

Furthermore, the silicon oxide film described in the present embodimentis not limited to a silicon dioxide (SiO₂) film, and may also be asilicon oxide film formed using the CVD method with silane and TEOS(tetraethylorthosilicate) as raw materials, or a silicon oxide filmformed using the polysiloxane (PSX) coating method. In addition, thesilicon oxide film may also contain other elements such as boron andphosphor.

[Effects]

According to the embodiment described above, within the process liquid15 containing the fluorine ions 24, the work surface of the work piece12 (the silicon oxide film 21) is brought into contact with the surfaceof the solid plate 11 onto which the hydrogen ions 23 are adsorbed.Accordingly, the work surface of the silicon oxide film 21 which is incontact with the solid plate 11 is chemically dissolved, and the worksurface is planarized. In other words, the silicon oxide film 21 can beplanarized using only a chemical reaction without mechanical polishing.Therefore, the abrasion damage to the work surface of the silicon oxidefilm 21, which occurs due to the mechanical polishing, can besuppressed.

Incidentally, if both the hydrogen ions and the fluorine ions arepresent, the hydrogen ions and the fluorine ions can be reacted with thesilicon oxide film to dissolve the silicon oxide film. Therefore, byimmersing the silicon oxide film in a hydrofluoric acid solution, thesilicon oxide film and the hydrofluoric acid solution can be reactedwith one another. However, if the silicon oxide film is only immersed inthe hydrofluoric acid solution, the silicon oxide film is processedisotropically and the work surface may not be planarized.

In contrast, in the present embodiment, the silicon oxide film 21 isimmersed in the process liquid 15 containing the fluorine ions 24 whichdo not react by immersion only, and the work surface is brought intocontact or extremely close proximity with the surface of the solid plate11 containing the hydrogen ions 23. Accordingly, the work surface of thesilicon oxide film 21 can be planarized by reacting only the worksurface of the silicon oxide film 21 which is in contact or extremelyclose proximity with the surface of the solid plate 11.

Second Embodiment

The planarization apparatus according to the present embodiment will bedescribed using FIGS. 4 and 5.

[Planarization Apparatus]

FIG. 4 is a perspective view showing a configuration example of aplanarization apparatus which planarizes a silicon oxide film accordingto the second embodiment. In the second embodiment, the process liquid15 is not stored in the container 10 as in the first embodiment, and theprocess liquid 15 is supplied onto the solid plate 11 through a supplyport 25. The solid plate 11 has a diameter of at least twice or morethan the size of the work piece 12 and can move rotationally. The supplyport 25 is arranged on the upstream side in the rotational direction ofthe work piece 12. The other configurations and the planarization methodare the same as in the planarization apparatus of the first embodimentshown in FIG. 1.

FIG. 5 is a plan view showing the configuration example of theplanarization apparatus which planarizes a silicon oxide film accordingto the second embodiment. As shown in FIG. 5, the supply port 25 isprovided on the upstream side of the work piece 12 in relation to therotational direction of the solid plate 11. Accordingly, the processliquid 15 can be efficiently supplied to a polishing portion of the workpiece 12. In addition, as shown in FIG. 5, a plurality of the supplyports 25 may also be provided in a row. An acidic solution containingfluorine ions, for example, is used as the process liquid 15.Accordingly, after the reaction of Chem. (1), even if a location ispresent in which the re-adsorption of the hydrogen ions 23 and the solidacidic catalyst 22 is insufficient, a fresh acidic solution is suppliedonto the solid acidic catalyst 22 before the process liquid 15 makescontact with the work piece 12 again, and a sufficient amount ofhydrogen ions can be adsorbed.

[Effects]

In the present embodiment, the silicon oxide film 21 is immersed in theprocess liquid 15 containing the fluorine ions 24 which do not react byimmersion only, and the work surface is brought into contact orextremely close proximity with the surface of the solid plate 11containing the hydrogen ions 23. Accordingly, the work surface of thesilicon oxide film 21 can be planarized by reacting only the worksurface of the silicon oxide film 21 which is in contact or extremelyclose proximity with the surface of the solid plate 11.

In addition, according to the present embodiment, the process liquid 15,which has few impurities and a high purity, can always be supplied ontothe solid plate 11. Therefore, the work piece 12 can be polished withoutthe reaction products impeding the adsorption of the solid acidiccatalyst 22 and the hydrogen ions 23, or the reaction of Chem. (1).

Furthermore, the usage amount of the process liquid 15 can be reduced incomparison with the method where the process liquid 15 is stored in thecontainer 10 by adjusting the flow amount of the process liquid 15.

Application Example

[Application]

The application example of the planarization methods according to thefirst embodiment and the second embodiment will be described using FIGS.6 to 9. The planarization method according to these embodiments can beapplied to the Shallow Trench Isolation (STI) formation process of asemiconductor device.

FIGS. 6 to 9 are cross section views showing the STI formation processof a semiconductor device according to the present embodiment.

First, as shown in FIG. 6, for example, a tunnel insulating film 41containing a silicon oxide film or a silicon nitrate film is formed on asemiconductor substrate 40 using the Chemical Vapor Deposition (CVD)method. A charge storage film 42 containing a poly-crystalline siliconor an amorphous silicon is formed on the tunnel insulating film 41using, for example, the CVD method.

Next, as shown in FIG. 7, a groove 43 is formed in the charge storagefilm 42, the tunnel insulating film 41 and the semiconductor substrate40 using lithography and RIE (Reactive Ion Etching). The groove 43 isformed passing through the charge storage film 42 and the tunnelinsulating film 41 so as to remove a portion of the semiconductorsubstrate 40.

Next, as shown in FIG. 8, an element isolation insulating film 44containing a silicon oxide film on the whole surface thereof is formedusing, for example, the CVD method. Accordingly, the element isolationinsulating film 44 is embedded within the groove 43, and is also formedon the charge storage film 42 outside the groove 43.

Next, as shown in FIG. 9, the element isolation insulating film 44formed on the charge storage film 42 outside the groove 43 is removed.At this time, the planarization method of the silicon oxide filmaccording to the above embodiments described above is used. Morespecifically, a surface of the element isolation insulating film 44 isbrought into contact with the surface of the solid plate 11 onto whichthe hydrogen ions 23 are adsorbed, while immersing the surface of theelement isolation insulating film 44 in the process liquid 15. In otherwords, the above planarization method is performed with the surface ofthe element isolation insulating film 44 containing the silicon oxidefilm as the work surface. Accordingly, the element isolation insulatingfilm 44, the process liquid 15 and the hydrogen ions 23 react with oneanother. As a result, the element isolation insulating film 44 formed onthe charge storage film 42 outside the groove 43 can be removed whileplanarizing the surface of the element isolation insulating film 44.

In such a manner, the STI structure is formed in the applicationexample.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the inventions. Indeed, the novel embodiments described hereinmay be embodied in a variety of other forms; furthermore, variousomissions, substitutions and changes in the form of the embodimentsdescribed herein may be made without departing from the spirit of theinventions. The accompanying claims and their equivalents are intendedto cover such forms or modifications as would fall within the scope andspirit of the inventions.

What is claimed is:
 1. A planarization apparatus comprising: a solidplate containing a solid acidic catalyst which is an acidic cationexchanger having a functioning group with an acid dissociation constantof 1.0×10⁻³ or less; a process liquid supply unit which is configured tosupply a process liquid; and a maintaining portion which is configuredto hold a work piece and is configured to bring a work surface of thework piece and a surface of the solid plate into contact or extremelyclose proximity with one another in the process liquid.
 2. Theplanarization apparatus according to claim 1, further comprising: a heatsource connecting to the solid plate to adjust a temperature of the workpiece.
 3. The planarization apparatus according to claim 1, wherein thesolid plate is configured to be rotatable or slidable.
 4. Theplanarization apparatus according to claim 1, wherein the maintainingportion is configured to be rotatable or slidable.
 5. The planarizationapparatus according to claim 1, wherein the work piece contains asilicon oxide film, wherein the process liquid contains fluorine ions,and wherein the fluorine ions react with the work piece in accordancewith a chemical equation of SiO₂+6F⁻+6H⁺→SiF6²⁻+2H⁺+2H₂O.
 6. Theplanarization apparatus according to claim 5, wherein the process liquidis a sodium fluoride aqueous solution, a potassium fluoride aqueoussolution, an ammonium fluoride aqueous solution, or a mixed solution ofthe above and a hydrogen fluoride aqueous solution.
 7. A planarizationapparatus comprising: a rotatable solid plate containing a solid acidiccatalyst which is an acidic cation exchanger having a functioning groupwith an acid dissociation constant of 1.0×10⁻³ or less; a process liquidsupply unit which is configured to supply a process liquid onto therotatable solid plate; and a maintaining portion which is configured tohold a work piece and is configured to bring a work surface of the workpiece and a surface of the solid plate into contact or extremely closeproximity with one another where the process liquid is supplied to anupper stream side of the rotatable solid plate to flow to the workpiece.
 8. The planarization apparatus according to claim 7, furthercomprising: a heat source connecting to the solid plate to adjust atemperature of the work piece.
 9. The planarization apparatus accordingto claim 7, wherein the process liquid supply unit has a port such thatthe process liquid is supplied onto the solid plate through the port.10. The planarization apparatus according to claim 7, wherein theprocess liquid supply unit has a plurality of ports such that theprocess liquid is supplied onto the solid plate through the plurality ofthe ports.
 11. The planarization apparatus according to claim 7, whereina diameter of the solid plate is at least twice or more than a diameterof the work piece.
 12. The planarization apparatus according to claim 7,wherein the work piece contains a silicon oxide film, wherein theprocess liquid contains fluorine ions, and wherein the fluorine ionsreact with the work piece in accordance with a chemical equation ofSiO₂+6F⁻+6H⁺→SiF6²⁻+2H⁺+2H₂O.
 13. The planarization apparatus accordingto claim 12, wherein the process liquid is a sodium fluoride aqueoussolution, a potassium fluoride aqueous solution, an ammonium fluorideaqueous solution, or a mixed solution of the above and a hydrogenfluoride aqueous solution.